US4492600A - Corrosion-inhibiting paints and lacquers - Google Patents
Corrosion-inhibiting paints and lacquers Download PDFInfo
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- US4492600A US4492600A US06/398,226 US39822682A US4492600A US 4492600 A US4492600 A US 4492600A US 39822682 A US39822682 A US 39822682A US 4492600 A US4492600 A US 4492600A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/08—Intercalated structures, i.e. with atoms or molecules intercalated in their structure
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Definitions
- This invention relates to corrosion-inhibiting pigments based on intercalation compounds, to processes for the production thereof and to the use thereof.
- Active anti-corrosion pigments of major practical significance are red lead, zinc potassium chromate, zinc dust and zinc phosphate.
- Lead pigments are primarily used for long-term corrosion prevention, while chromates are more suitable for short-term corrosion prevention.
- zinc dust paints involve considerable processing problems.
- the zinc phosphate pigments hitherto recommended as corrosion-inhibiting pigments have corrosion-inhibiting properties significantly inferior to those of previously used zinc potassium chromate pigments.
- organic corrosion inhibitors of the type preferably used hitherto in aqueous systems has often been complicated by the solubility levels in the lacquer, above all in the cases where the inhibitors have been used in the form of salts.
- An object of the present invention is to develop new active corrosion-inhibiting pigments which, so far as the corrosion-inhibiting effect thereof is concerned, are at least equivalent to known corrosion-inhibiting pigments and which do not have the disadvantages of known corrosion-inhibiting pigments.
- composition pigments consisting of an inorganic matrix and, intercalated therein organic substances corresponding to the following formula: ##EQU2## wherein Me(II) represents one or more divalent metals;
- Me(III) represents one or more trivalent metals
- A represents one or more anhydrides of inorganic acids
- I represents one or more organic compounds
- aq represents from 0.5 to 9 moles, preferably from 0.75 to 4 moles, of water
- x, y and z are whole or fractional numbers, of which
- x has values of from 0 to 1
- y has values of from 0 to 0.7
- z has values of from greater than 0 to 0.4;
- a specific surface according to BET which means the surface area of the corrosion-inhibiting pigments of this invention was determined by the Brunauer-Emmett-Teller equation of determining surface areas by the surface adsorption of Nitrogen (J. Americ. Chem. Soc. 60, 309 (1938)), of from 0.1 to 200 m 2 /g, preferably from 1 to 150 m 2 /g and a content of water soluble components of less than 0.6 %, preferably less than 0.3 %.
- the divalent metals may be one or more of the metals selected from magnesium, calcium, strontium, barium, zinc, iron and manganese, while the trivalent metals may be one or more metals selected from aluminum iron, manganese and chromium.
- the combination of trivalent aluminum with the similarly colourless alkaline-earth metals and/or the zinc cation is particularly preferred because, providing the organic substances and also the inorganic anions are suitably selected, it is possible to obtain pigments having no tinting strength which may be coloured as required.
- the group of anhydrides of inorganic acids is formed from the oxides of boron, chromium, carbon, molybdenum, phosphorus and tungsten, carbon dioxide and phosphorus pentoxide being preferred. They may be used either individually or in combination.
- the organic substances in the above formula are one or more known organic corrosion inhibitors having the character of Lewis bases.
- the class of effective and intercalatable corrosion inhibitors includes higher amines, aldehydes, alcohols or ketones, amidines, guanidines, heterocyclic compounds containing nitrogen and/or oxygen and/or sulphur as hetero-atoms (urotropin, pyrazoles, imidazoles, imidazolines, oxazoles, isoxazoles, thiazoles, isothiazoles, triazoles, triazines, pyridines and the corresponding benzene-fused systems, such as benzimidazoles, benzothiazoles, benzotriazoles, quinolines or isoquinolines, quinazolines and others), sulphur-nitrogen compounds organic acetylene derivatives, organic nitro compounds and lignin derivatives (sulphonates).
- phosphonic acids and phosphonocarboxylic acids and derivatives and salts thereof, nitrogen-containing phosphonic or phosphono-carboxylic acids and derivatives and salts thereof, organic and inorganic salts of carboxylic acids, such as acetates, benzoates, cinnamates, salicylates, derivatives and salts of dicarboxylic acids and polycarboxylic acids and polyacrylates, derivatives of tannic acids, such as tannin and gallic acid, and synthetic aromatic phenolic hydroxy carboxylic acids and polymers or polyesters of phenolic hydroxy carboxylic acids.
- suitable mixtures of these compounds it is, of course, also possible to use suitable mixtures of these compounds.
- the solubility thereof in the binder may surprisingly be reduced to such a considerable extent that corrosion-inhibiting pigments having excellent processing properties are obtained.
- the corrosion-inhibiting pigments obtained in this way do not have the tendency towards bubble formation of the binder on exposure to weathering which is typical of readily soluble pigments and of pigments having an excessive salt content.
- organic compounds to be ultimately intercalated is determined essentially by the economy thereof and also by the particular applications envisaged. It is as preferred to use derivatives and salts of carboxylic acids and phosphonic acids as salts of benzoic acid, cinnamic acid, polycarboxylic acids and phosphonopropionic acids as well as tannin.
- the corrosion-inhibiting pigments according to the present invention contain water of crystallisation in a quantity of which the exact analytical determination involves difficulties because some very loosely bound water molecules are present. Thus, dehydration phenomena may occur at temperatures as low as 60° C. This relatively "volatile" water component depends to a very large extent upon the formulation conditions (drying temperature and drying time) and upon the crystallinity and particle size of the final corrosion-inhibiting pigment.
- Thermogravimetric analysis of the compounds shows that dehydration of the substances occurs over the relatively wide temperature range of from 60° to 240° C., while dehydroxylation takes place at temperatures above 160° C. in the case of substances rich in Me 2+ (in which case there may be smooth transitions between dehydration and dehydroxylation), and at temperatures above 280° C. in the case of substances having x-values of from 0.2 to 0.6.
- a second dehydroxylation step takes place at temperatures above 400° C.
- the present invention also relates to processes for producing corrosion-inhibiting pigments corresponding to the following general formula: ##EQU4##
- the inorganic anions and the organic inhibitors may be initially introduced together either during or after precipitation or may even be added after separation of the mother liquor of the host lattice.
- the corrosion-inhibiting pigments according to the present invention have a pH of greater than 6, preferably from 7.0 to 8.5.
- Starting compounds suitable for use in the production of the corrosion-inhibiting pigments according to the present invention include, in the case of the divalent metals, the hydroxides, hydroxy salts, carbonates, basic carbonates, nitrates, chlorides, formates, acetates, oxalates and other organic compounds thereof, as well as the active oxides thereof.
- the metals Zn, Mg, Mn and Fe may also be used in the form of the sulphates thereof, in addition to which Zn may be used in the form of an alkali metal zincate.
- the trivalent metals may be used in the form of oxide-hydroxides, hydroxides, hydroxy salts, carbonates, basic carbonates, nitrates, chlorides, sulphates, formates, acetates, oxalates and organic carboxylates.
- sulphates should not be used because otherwise substantially insoluble alkaline earth metal sulphates are also formed.
- Suitable precipitants are substances having an alkaline reaction preferably sodium hydroxide, soda, ammonia, ammonium-carbonate or mixtures thereof.
- a pH of greater than 6.0, preferably from 7 to 9 should be adjusted, the final pH being variable in dependence upon the metal ions used and the final corrosion-inhibiting pigment having a DIN pH of greater than 6, preferably from 7 to 8.5.
- the quantity in which these metals are used is selected in such a way that the pH of the corrosion-inhibiting pigment obtained is no higher than 12, preferably no higher than 10. With increasing basicity from calcium via strontium and barium, the content of these alkaline earth metals in the inorganic matrix has to be reduced.
- the pH of the corrosion-inhibiting pigments is determined in accordance with DIN 53 200, the pH of a suspension of the pigment prepared in a specific manner being measured.
- the corrosion-inhibiting pigments according to the present invention have specific surfaces according to BET (G. Brunauer, P. H. Emmet and H. Teller, J. Amer. Chem. Soc. 60, 309 (1938)) of from 0.1 to 200 m 2 /g, preferably from 1.0 to 150 m 2 /g.
- BET Brunauer, P. H. Emmet and H. Teller, J. Amer. Chem. Soc. 60, 309 (1938)
- the water-soluble components are quoted in accordance with DIN 53 197.
- the corrosion-inhibiting test of the pigments according to the present invention was carried out by the salt spray test according to the SS SIN 50 021 (long term spraying with a 5% common salt solution at 35 ⁇ 2° C.).
- the coatings were applied to phosphated steel plates (phosphating process: Bonder 101 of Metallgesellschaft, Frankfurt) and to degreased, bright steel plates.
- the primer was applied by spraying.
- the following standard test formulation was used:
- the results of the corrosion-inhibition testing of the test pigments and comparison pigments are set out in Table 1.
- the pigments were evaluated in accordance with the following scheme: samples were regularly taken over the test period, the steel plates receiving marks ranging from 0 (no damage) to 12 (complete destruction of the coating). The sum of the individual marks awarded to each plate gives the degree of corrosion which is then greater, the poorer the corrosion-inhibiting power of the coating.
- the corrosion-inhibiting effect of the corrosion-inhibiting pigments according to the present invention is distinctly supeerior to that of the other divalent and trivalent metal salts used. In addition, despite minimal slow-release properties, they do not show the bubble formation in lacquers which is typical of soluble pigments.
- the present invention is illustrated by the following Examples.
- Example 3 The procedure is as in Example 3, except that 29.2 g of polycarboxylic acid (Belgard EV, a Ciba-Geigy product) are added instead of the phosphonopropionic acid.
- Polycarboxylic acid Belgard EV, a Ciba-Geigy product
- the suspension which still shows a strongly acid reaction (pH 5.3) is then adjusted to pH 8.5 with 166.7 ml of a 2.0 molar Na 1 .56 Al(OH) 4 .56 - solution, followed by stirring for another hour at 80° C., filtration, washing and drying at 105° C.
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Abstract
This invention relates to corrosion-inhibiting paints and lacquers containing pigments comprising an organic corrosion inhibitor intercalated into an inorganic matrix said pigment having the formula wherein ##EQU1## wherein Me(II)O is at least one divalent metal oxide;
Me(III)2 O3 is at least one trivalent metal oxide;
A is at least one inorganic acid anhydride;
I is at least one organic corrosion inhibitor;
aq is from 0.5 to 9 moles of water; and
x, y and z are whole or fractional numbers and
x has a value of from 0 to 1,
y has a value of from 0 to 0.7 and
z has a value of from greater than 0 to 0.4,
with the proviso that the organic corrosion inhibitor is at least 0.5% by weight of inorganic material a process for the production of these pigments and their use in paints, lacquers and lubricants.
Description
This invention relates to corrosion-inhibiting pigments based on intercalation compounds, to processes for the production thereof and to the use thereof.
Active anti-corrosion pigments of major practical significance are red lead, zinc potassium chromate, zinc dust and zinc phosphate.
Lead pigments are primarily used for long-term corrosion prevention, while chromates are more suitable for short-term corrosion prevention. In view of the high zinc metal contents required (up to 98%, by weight), zinc dust paints involve considerable processing problems. The zinc phosphate pigments hitherto recommended as corrosion-inhibiting pigments have corrosion-inhibiting properties significantly inferior to those of previously used zinc potassium chromate pigments.
The use of organic corrosion inhibitors of the type preferably used hitherto in aqueous systems, for example in water circuits, has often been complicated by the solubility levels in the lacquer, above all in the cases where the inhibitors have been used in the form of salts.
Accordingly, there is a considerable interest in new corrosion-inhibiting pigments which do not have the disadvantages of known corrosion-inhibiting pigments, or in new corrosion-inhibiting pigments which are active over a broader spectrum in combination with known corrosion-inhibiting pigments.
An object of the present invention is to develop new active corrosion-inhibiting pigments which, so far as the corrosion-inhibiting effect thereof is concerned, are at least equivalent to known corrosion-inhibiting pigments and which do not have the disadvantages of known corrosion-inhibiting pigments.
Materials which satisfy these requirements particularly effectively are composition pigments consisting of an inorganic matrix and, intercalated therein organic substances corresponding to the following formula: ##EQU2## wherein Me(II) represents one or more divalent metals;
Me(III) represents one or more trivalent metals;
A represents one or more anhydrides of inorganic acids;
I represents one or more organic compounds;
aq represents from 0.5 to 9 moles, preferably from 0.75 to 4 moles, of water; and
x, y and z are whole or fractional numbers, of which
x has values of from 0 to 1,
y has values of from 0 to 0.7 and
z has values of from greater than 0 to 0.4;
with the proviso that at least 0.5%, by weight, preferably more than 1.0%, by weight, of organic substance, based on the inorganic component, is present.
In one particular effective form, they have a specific surface according to BET which means the surface area of the corrosion-inhibiting pigments of this invention was determined by the Brunauer-Emmett-Teller equation of determining surface areas by the surface adsorption of Nitrogen (J. Americ. Chem. Soc. 60, 309 (1938)), of from 0.1 to 200 m2 /g, preferably from 1 to 150 m2 /g and a content of water soluble components of less than 0.6 %, preferably less than 0.3 %.
In the formula: ##EQU3## the divalent metals may be one or more of the metals selected from magnesium, calcium, strontium, barium, zinc, iron and manganese, while the trivalent metals may be one or more metals selected from aluminum iron, manganese and chromium.
The combination of trivalent aluminum with the similarly colourless alkaline-earth metals and/or the zinc cation is particularly preferred because, providing the organic substances and also the inorganic anions are suitably selected, it is possible to obtain pigments having no tinting strength which may be coloured as required.
The group of anhydrides of inorganic acids is formed from the oxides of boron, chromium, carbon, molybdenum, phosphorus and tungsten, carbon dioxide and phosphorus pentoxide being preferred. They may be used either individually or in combination.
The organic substances in the above formula are one or more known organic corrosion inhibitors having the character of Lewis bases.
A full review of this class of substances may be found in Articles in Chemikerzeitung No. 6 (1976), pages 247 to 262, DEFAZET No. 4 (1971), pages 155 to 162, loc cit No. 5, pages 213 to 223, loc cit No. 6, pages 257 to 266, loc cit No. 7, pages 310 to 319, loc cit No. 8, pages 361 to 367, and in the book entitled "Corrosion Inhibitors" by M. W. Ranney (Noyes DATA Co. 1976). Accordingly, the class of effective and intercalatable corrosion inhibitors includes higher amines, aldehydes, alcohols or ketones, amidines, guanidines, heterocyclic compounds containing nitrogen and/or oxygen and/or sulphur as hetero-atoms (urotropin, pyrazoles, imidazoles, imidazolines, oxazoles, isoxazoles, thiazoles, isothiazoles, triazoles, triazines, pyridines and the corresponding benzene-fused systems, such as benzimidazoles, benzothiazoles, benzotriazoles, quinolines or isoquinolines, quinazolines and others), sulphur-nitrogen compounds organic acetylene derivatives, organic nitro compounds and lignin derivatives (sulphonates).
It is particularly preferred to use phosphonic acids and phosphonocarboxylic acids and derivatives and salts, thereof, nitrogen-containing phosphonic or phosphono-carboxylic acids and derivatives and salts thereof, organic and inorganic salts of carboxylic acids, such as acetates, benzoates, cinnamates, salicylates, derivatives and salts of dicarboxylic acids and polycarboxylic acids and polyacrylates, derivatives of tannic acids, such as tannin and gallic acid, and synthetic aromatic phenolic hydroxy carboxylic acids and polymers or polyesters of phenolic hydroxy carboxylic acids. However, it is, of course, also possible to use suitable mixtures of these compounds.
By intercalating these compounds, known collectively as strongly hydrophilic organic reagents, in the inorganic matrix, the solubility thereof in the binder may surprisingly be reduced to such a considerable extent that corrosion-inhibiting pigments having excellent processing properties are obtained. For example, the corrosion-inhibiting pigments obtained in this way do not have the tendency towards bubble formation of the binder on exposure to weathering which is typical of readily soluble pigments and of pigments having an excessive salt content.
The choice of the organic compounds to be ultimately intercalated is determined essentially by the economy thereof and also by the particular applications envisaged. It is as preferred to use derivatives and salts of carboxylic acids and phosphonic acids as salts of benzoic acid, cinnamic acid, polycarboxylic acids and phosphonopropionic acids as well as tannin.
It is pointed out that the corrosion-inhibiting pigments according to the present invention contain water of crystallisation in a quantity of which the exact analytical determination involves difficulties because some very loosely bound water molecules are present. Thus, dehydration phenomena may occur at temperatures as low as 60° C. This relatively "volatile" water component depends to a very large extent upon the formulation conditions (drying temperature and drying time) and upon the crystallinity and particle size of the final corrosion-inhibiting pigment.
Thermogravimetric analysis of the compounds shows that dehydration of the substances occurs over the relatively wide temperature range of from 60° to 240° C., while dehydroxylation takes place at temperatures above 160° C. in the case of substances rich in Me2+ (in which case there may be smooth transitions between dehydration and dehydroxylation), and at temperatures above 280° C. in the case of substances having x-values of from 0.2 to 0.6. In the case of the pigments rich in Me3+, a second dehydroxylation step takes place at temperatures above 400° C.
The present invention also relates to processes for producing corrosion-inhibiting pigments corresponding to the following general formula: ##EQU4## In one of these processes, it is possible to precipitate a divalent and/or trivalent metal salt solution in the required ratio with equivalent quantities or an excess of alkalis, optionally in conjunction with alkali metallates, normally, inversely or simultaneously at temperatures of up to 100° C., preferably at temperatures of from 50° to 100° C. The inorganic anions and the organic inhibitors may be initially introduced together either during or after precipitation or may even be added after separation of the mother liquor of the host lattice.
In a second process, basic salts of thedivalent and/or trivalent metals with the acid form of the inorganic and, optionally, organic ions are treated in air at temperatures of up to 100° C., preferably at temperatures of from 50° to 100° C. and, optionally after alkalisation, are heated in an autoclave for up to 12 hours at temperatures of up to 220° C.
It is, of course, also possible to use combinations of the two production processes, in which case salts of the inorganic and organic ions may also be used. In this case, the alkali should be used in such quantities that the corrosion-inhibiting pigments according to the present invention have a pH of greater than 6, preferably from 7.0 to 8.5.
Starting compounds suitable for use in the production of the corrosion-inhibiting pigments according to the present invention include, in the case of the divalent metals, the hydroxides, hydroxy salts, carbonates, basic carbonates, nitrates, chlorides, formates, acetates, oxalates and other organic compounds thereof, as well as the active oxides thereof. The metals Zn, Mg, Mn and Fe may also be used in the form of the sulphates thereof, in addition to which Zn may be used in the form of an alkali metal zincate. The trivalent metals may be used in the form of oxide-hydroxides, hydroxides, hydroxy salts, carbonates, basic carbonates, nitrates, chlorides, sulphates, formates, acetates, oxalates and organic carboxylates. However, if Ca-, Sr- and/or Ba-salts are used in combination with the trivalent metals, sulphates should not be used because otherwise substantially insoluble alkaline earth metal sulphates are also formed. Suitable precipitants are substances having an alkaline reaction preferably sodium hydroxide, soda, ammonia, ammonium-carbonate or mixtures thereof. According to the present invention, a pH of greater than 6.0, preferably from 7 to 9, should be adjusted, the final pH being variable in dependence upon the metal ions used and the final corrosion-inhibiting pigment having a DIN pH of greater than 6, preferably from 7 to 8.5.
It is advantageous to carry out precipitation with an excess of alkalis. This leads to excellent crystalline corrosion-inhibiting pigments. In the case of the heavy elements of Group IIa (Ca, Sr and Ba), only a few percent should be used because otherwise the binders may be readily hydrolysed and ultimately destroyed through excessive basicity. Accordingly, the quantity in which these metals are used is selected in such a way that the pH of the corrosion-inhibiting pigment obtained is no higher than 12, preferably no higher than 10. With increasing basicity from calcium via strontium and barium, the content of these alkaline earth metals in the inorganic matrix has to be reduced.
The pH of the corrosion-inhibiting pigments is determined in accordance with DIN 53 200, the pH of a suspension of the pigment prepared in a specific manner being measured. The corrosion-inhibiting pigments according to the present invention have specific surfaces according to BET (G. Brunauer, P. H. Emmet and H. Teller, J. Amer. Chem. Soc. 60, 309 (1938)) of from 0.1 to 200 m2 /g, preferably from 1.0 to 150 m2 /g. The water-soluble components are quoted in accordance with DIN 53 197.
The corrosion-inhibiting test of the pigments according to the present invention was carried out by the salt spray test according to the SS SIN 50 021 (long term spraying with a 5% common salt solution at 35±2° C.). The coatings were applied to phosphated steel plates (phosphating process: Bonder 101 of Metallgesellschaft, Frankfurt) and to degreased, bright steel plates. The primer was applied by spraying. The following standard test formulation was used:
______________________________________
Binder: Alkydal F 67 (a long-oil, fatty-acid-
modified alkyd resin)
Main pigment: Bayertitan A
Pigmenting level:
PVK 32%
Mixing ratio: Main pigment to active pigment
80:15%, by weight
Grinding: Vibrating ball mill
Required particle
At least below 25 μm
fineness:
Processing: Spraying (conventional)
______________________________________
Two coating supports:
a. normal steel plates of the type normally used in a lacquer industry, bright and very carefully degreased,
b. phosphated steel plates (process: Bonder 101 of Metallgesellschaft, Frankfurt).
The results of the corrosion-inhibition testing of the test pigments and comparison pigments are set out in Table 1. The pigments were evaluated in accordance with the following scheme: samples were regularly taken over the test period, the steel plates receiving marks ranging from 0 (no damage) to 12 (complete destruction of the coating). The sum of the individual marks awarded to each plate gives the degree of corrosion which is then greater, the poorer the corrosion-inhibiting power of the coating.
The corrosion-inhibiting effect of the corrosion-inhibiting pigments according to the present invention is distinctly supeerior to that of the other divalent and trivalent metal salts used. In addition, despite minimal slow-release properties, they do not show the bubble formation in lacquers which is typical of soluble pigments.
They are therefore eminently suitable for use in corrosion-inhibiting paints, lacquers and lubricants.
The present invention is illustrated by the following Examples.
986.3 g of basic zinc carbonate (33.0%, by weight, of ZnO) are stirred into 2 liters of water and heated to 70° C. 7.65 g of 99.8%, by weight, benzoic acid are then added to the suspension, followed by the introduction over a period of 30 minutes of 500 ml of Na2 Al(OH)5 -solution (1.0 mole of Al2 O3 /l) [pH 11.8]. The pH is then reduced to 9.5 by the addition of 28.82 g of 85%, by weight, phosphoric acid, followed by stirring for 1 hour at 70° C., filtration, washing and drying at 110° C. ##EQU5## x: 0.8 y1 : 0.025
y2 : 0.15
z: 0.0125 (corresponds to approximately 1.4%, by weight)
aq: 0.86
Reactants:
basic zinc carbonate
sodium aluminate
phosphoric acid
benzoic acid
Pigment-specific data:
______________________________________
BET-surface 35.0 m.sup.2 /g
Density 3.05 g/cc
Water-soluble fractions
0.22%
______________________________________
______________________________________
Analysis %, by weight
______________________________________
ZnO 63.9 (0.803)
Al.sub.2 O.sub.3
10.0 (0.1)
P.sub.2 O.sub.5
3.5 (0.0252)
C inorg. 1.7 (0.145)
C org. 1.0 (0.0122)
H.sub.2 O 15.2 (0.86)
______________________________________
739.7 g of basic zinc carbonate having a ZnO-content of 33.0%, by weight, and 156.0 g of alumina hydrate (65.36%, by weight, of Al2 O3), corresponding to a mixing ratio of Zn to Al of 3:2, are thoroughly mixed and made into a paste with a little water. 86.47 g of 85%, by weight, phosphoric acid and 32.1 g of 40%, by weight, phosphonopropionic acid are then added. The resulting reaction mixture is tempered in an autoclave for 4 hours at 190° C. (pressure: 14 bars) and the moist end product is dried at 110° C.
System: ##EQU6## x: 0.6 y1 : 0.075
y2 : 0.1
z: 0.01667 (corresponds to approximately 2.5%, by weight)
aq: 1.1
Pigment-specific data:
______________________________________
BET-surface 24.0 m.sup.2 /g
Density 2.09 g/cc
Water-soluble fractions
0.41%
______________________________________
______________________________________
Analysis: %, by weight
______________________________________
ZnO 47.5 (0.597)
Al.sub.2 O.sub.3
20.1 (0.202)
P.sub.2 O.sub.5
10.5 (0.0756)
C inorg. 1.1 (0.0936)
C org. 0.58 (0.0164)
H.sub.2 O 19.4 (1.1)
______________________________________
1232.9 g of basic zinc carbonate (ZnO-content 33.0%) are stirred into 1200 ml of water and heated to 70° C. 172.93 g of 85%, by weight, phosphoric acid and 38.53 g of 40%, by weight, phosphonopropionic acid are then added over periods of 10 minutes. The reaction is over after stirring for 4 hours at 70° C. and the product may be filtered off, washed and dried at 110° C.
System: x ZnO.y1 P2 O5.y2 CO2.z phosphonopropionic acid.aq
x: 1
y1 : 0.15
y2 : 0.19
z: 0.02 (corresponds to 2.4%, by weight)
aq: 0.87
Pigment-specific data:
______________________________________
BET-surface 34.0 m.sup.2 /g
Density 3.26 g/cc
Water-soluble fractions
0.17%
______________________________________
______________________________________
Analysis %, by weight
______________________________________
ZnO 62.1 (1.0)
P.sub.2 O.sub.5
16.1 (0.149)
C inorg. 1.7 (0.186)
C org. 0.54 (0.0196)
H.sub.2 O 12.0 (0.871)
______________________________________
The procedure is as in Example 3, except that 29.2 g of polycarboxylic acid (Belgard EV, a Ciba-Geigy product) are added instead of the phosphonopropionic acid.
System: x ZnO.y1 P2 O5.y2 CO2.z polycarboxylic acid.aq
x: 1
y1 : 0.15
y2 : 0.19
z: 4.4%, by weight, based on inorganic matrix
aq: 0.87
Pigment-specific data:
______________________________________
BET-surface 45 m.sup.2 /g
Density 3.58 g/cc
Water-soluble fractions
0.19%
______________________________________
______________________________________
Analysis %, by weight
______________________________________
ZnO 60.4 (1.002)
P.sub.2 O.sub.5
15.5 (0.147)
C inorg. 1.8 (0.186)
C org. 2.44 (4.69)
H.sub.2 O 12.5 (0.86)
______________________________________
3.7 liters of water are added to 739.7 g of basic zinc carbonate containing 33.0%, by weight, of ZnO and the resulting suspension heated with stirring to 80° C. 76.86 g of 85%, by weight, phosphoric acid and 20.18 g of 50%, by weight, of polyacrylic acid (POC-HS 2020, a Degussa product) having an average molecular weight of 1500 are then added dropwise over a period of 30 minutes, followed by stirring for 2 hours at 80° C. The suspension which still shows a strongly acid reaction (pH 5.3) is then adjusted to pH 8.5 with 166.7 ml of a 2.0 molar Na1.56 Al(OH)4.56 - solution, followed by stirring for another hour at 80° C., filtration, washing and drying at 105° C.
System: ##EQU7## x: 0.9 y1 : 0.1
y2 : 0.2
z: 0.00667 (corresponds to approximately 2.4%, by weight)
aq: 1.25
Pigment specific data:
______________________________________
BET-surface 53.0 m.sup.2 /g
Density 2.39 g/cc
Water-soluble fractions
0.31%
______________________________________
______________________________________
Analysis %, by weight
______________________________________
ZnO 57.7 (0.903)
Al.sub.2 O.sub.3
4.0 (0.050)
P.sub.2 O.sub.5
10.9 (0.098)
C inorg. 2.0 (0.212)
C org. 1.1 (0.0019)
H.sub.2 O 17.6 (1.24)
______________________________________
Two solutions, one consisting of 763.4 ml with 1.31 moles of MgSO4 /1 and 0.0375 mole of (NH4) Mo7 O24 /1 and the second of 794.9 ml of ZnSo4 -solution (1.95 moles of ZnSo4 /1) are simultaneously added to 2000 ml of a sodium aluminate/zincate solution (0.5 mole of Al2 O3 /1; 0.12 mole of ZnO/1) tempered to 90° C. A final pH of 8.5 is then adjusted with a 45%, by weight sodium hydroxide solution. The temperature of the reaction solution should not fall below 80° C. during the addition. After precipitating the product is stirred for another 2 hours at 90° C. It is then filtered off while hot, washed, the filter cake re-suspended and 62.0 g of zinc benzoate (99.3%, by weight) and 46.1 g of 85%, by weight, phosphoric acid added. Any excessive reduction in pH is corrected with a little (final pH: 8.5). The suspension is then stirred for 2 hours at room temperature, subsequently filtered, washed free from salts and the filter cake dried at 110° C.
System: ##EQU8## x1 : 0.4 x2 : 0.2
y1 : 0.04
y2 : 0.04
z: 0.08 (corresponds to 8.25%, by weight)
aq: 1.5
Pigment-specific data:
______________________________________
BET-surface 41.0 m.sup.2 /g
Density 2.5 g/cc
water-soluble fractions
0.32%
______________________________________
______________________________________
Analysis %, by weight
______________________________________
ZnO 27.7 (0.407)
MgO 6.6 (0.196)
Al.sub.2 O.sub.3
17.4 (0.204)
MoO.sub.3 4.8 (0.040)
P.sub.2 O.sub.5
4.8 (0.040)
C org. 5.25 (0.075)
H.sub.2 O 31.2 (1.51)
______________________________________
TABLE 1
______________________________________
Corrosion inhibition results according to SS
DIN 50 021
Example No. or Bonder 101
Steel plate
Product name DC* DC*
______________________________________
1 12.0 23.5
2 14.0 22.0
3 8.0 14.0
4 4.5 16.5
5 6.0 24.0
6 10.0 14.5
Zinc chromate 4.5 19.0
Zinc phosphate 17.5 27.5
______________________________________
*degree of corrosion = sum of 6 evaluations (duration of salt spray test:
744 hours).
Claims (1)
1. Corrosion-inhibiting paints and lacquers pigmented with a corrosion-inhibiting pigment having a specific surface according to BET of from 0.1 to 200 m2 /g, a content of water-soluble components of less than 0.6%, and comprising an organic corrosion inhibitor intercalated into an inorganic matrix having the formula: ##EQU9## wherein Me(II)O is at least one divalent metal oxide;
ME(III)2 O3 is at least one trivalent metal oxide;
A is at least one inorganic acid anhydride;
I is at least one organic corrosion inhibitor;
aq is from 0.5 to 9 moles of water; and
x, y and z are whole or fractional numbers and
x has a value of from 0 to 1,
y has a value of from 0 to 0.7 and
z has a value of from greater than 0 to 0.4,
with the proviso that the organic corrosion inhibitor is at least 0.5% by weight of inorganic material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3128716 | 1981-07-21 | ||
| DE19813128716 DE3128716A1 (en) | 1981-07-21 | 1981-07-21 | ACTIVE CORROSION PROTECTION PIGMENTS, METHOD FOR THEIR PRODUCTION AND THEIR USE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4492600A true US4492600A (en) | 1985-01-08 |
Family
ID=6137354
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/398,226 Expired - Fee Related US4492600A (en) | 1981-07-21 | 1982-07-14 | Corrosion-inhibiting paints and lacquers |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4492600A (en) |
| EP (1) | EP0070455B1 (en) |
| JP (1) | JPS5825362A (en) |
| CA (1) | CA1191021A (en) |
| DE (2) | DE3128716A1 (en) |
| NO (1) | NO822359L (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4626283A (en) * | 1985-03-21 | 1986-12-02 | Engelhard Corporation | Corrosion and marine growth inhibiting compositions |
| US4774345A (en) * | 1985-03-21 | 1988-09-27 | Engelhard Corporation | Amine-complexed zinc salts of organic diacids |
| US5028489A (en) * | 1989-02-01 | 1991-07-02 | Union Oil Of California | Sol/gel polymer surface coatings and corrosion protection enhancement |
| US5158605A (en) * | 1989-02-01 | 1992-10-27 | Union Oil Company Of California | Sol/gel polymer surface coatings and corrosion protection enhancement |
| US5162413A (en) * | 1989-02-01 | 1992-11-10 | Union Oil Company Of California | Salt-containing surface coating polymer compositions and substrates coated therewith |
| US5166248A (en) * | 1989-02-01 | 1992-11-24 | Union Oil Company Of California | Sol/gel-containing surface coating polymer compositions |
| US5175202A (en) * | 1989-02-01 | 1992-12-29 | Union Oil Company Of California | Salt-containing glossy surface coating polymer compositions and substrates coated therewith |
| US5198487A (en) * | 1989-02-01 | 1993-03-30 | Union Oil Company Of California | Process for preparing salt-containing surface coating polymer compositions |
| USD821930S1 (en) | 2016-06-06 | 2018-07-03 | Axletech International Ip Holdings, Llc | Gearbox assembly for an axle |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0647659B2 (en) * | 1985-09-24 | 1994-06-22 | 協和化学工業株式会社 | Anticorrosion paint composition |
| JPH0615679B2 (en) * | 1987-05-02 | 1994-03-02 | 協和化学工業株式会社 | Anticorrosion paint composition |
| DE4206553A1 (en) * | 1992-03-02 | 1993-09-09 | Merck Patent Gmbh | CLATHRASIL OF THE STRUCTURAL TYPE DODEKASIL 1 H WITH A SMALL MEDIUM CRYSTAL SIZE |
| DE19507054A1 (en) * | 1995-03-01 | 1996-09-05 | Budenheim Rud A Oetker Chemie | Use of metal borophosphates and agents therefor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3137717A (en) * | 1956-06-02 | 1964-06-16 | Peters Kurt | Metal acid salts of polybasic organic acids |
| US3200136A (en) * | 1962-04-24 | 1965-08-10 | Beecham Res Lab | Metal chelates of alpha-hydroxy-carboxylic acids and their preparation |
| US3391176A (en) * | 1966-02-16 | 1968-07-02 | Beecham Res Lab | Chelate compounds and process for their preparation |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2071070B (en) * | 1979-02-03 | 1983-02-02 | British Petroleum Co | Corrosion inhibitors method of producing them and protective coatings containing them |
-
1981
- 1981-07-21 DE DE19813128716 patent/DE3128716A1/en not_active Withdrawn
-
1982
- 1982-07-06 NO NO822359A patent/NO822359L/en unknown
- 1982-07-07 DE DE8282106055T patent/DE3260897D1/en not_active Expired
- 1982-07-07 EP EP82106055A patent/EP0070455B1/en not_active Expired
- 1982-07-14 US US06/398,226 patent/US4492600A/en not_active Expired - Fee Related
- 1982-07-19 JP JP57124539A patent/JPS5825362A/en active Pending
- 1982-07-19 CA CA000407535A patent/CA1191021A/en not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3137717A (en) * | 1956-06-02 | 1964-06-16 | Peters Kurt | Metal acid salts of polybasic organic acids |
| US3200136A (en) * | 1962-04-24 | 1965-08-10 | Beecham Res Lab | Metal chelates of alpha-hydroxy-carboxylic acids and their preparation |
| US3391176A (en) * | 1966-02-16 | 1968-07-02 | Beecham Res Lab | Chelate compounds and process for their preparation |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4626283A (en) * | 1985-03-21 | 1986-12-02 | Engelhard Corporation | Corrosion and marine growth inhibiting compositions |
| US4774345A (en) * | 1985-03-21 | 1988-09-27 | Engelhard Corporation | Amine-complexed zinc salts of organic diacids |
| US5028489A (en) * | 1989-02-01 | 1991-07-02 | Union Oil Of California | Sol/gel polymer surface coatings and corrosion protection enhancement |
| US5158605A (en) * | 1989-02-01 | 1992-10-27 | Union Oil Company Of California | Sol/gel polymer surface coatings and corrosion protection enhancement |
| US5162413A (en) * | 1989-02-01 | 1992-11-10 | Union Oil Company Of California | Salt-containing surface coating polymer compositions and substrates coated therewith |
| US5166248A (en) * | 1989-02-01 | 1992-11-24 | Union Oil Company Of California | Sol/gel-containing surface coating polymer compositions |
| US5175202A (en) * | 1989-02-01 | 1992-12-29 | Union Oil Company Of California | Salt-containing glossy surface coating polymer compositions and substrates coated therewith |
| US5198487A (en) * | 1989-02-01 | 1993-03-30 | Union Oil Company Of California | Process for preparing salt-containing surface coating polymer compositions |
| USD821930S1 (en) | 2016-06-06 | 2018-07-03 | Axletech International Ip Holdings, Llc | Gearbox assembly for an axle |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3128716A1 (en) | 1983-02-10 |
| EP0070455B1 (en) | 1984-10-03 |
| CA1191021A (en) | 1985-07-30 |
| EP0070455A1 (en) | 1983-01-26 |
| NO822359L (en) | 1983-01-24 |
| JPS5825362A (en) | 1983-02-15 |
| DE3260897D1 (en) | 1984-11-08 |
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Legal Events
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| AS | Assignment |
Owner name: BAYER AKTIENGESELLSCHAFT LEVERKUSEN, GERMANY A COR Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:BRUNN, HORST;HUND, FRANZ;RAMBOLD, WOLFGANG;AND OTHERS;REEL/FRAME:004027/0340 Effective date: 19820708 |
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| FPAY | Fee payment |
Year of fee payment: 4 |
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| LAPS | Lapse for failure to pay maintenance fees | ||
| FP | Lapsed due to failure to pay maintenance fee |
Effective date: 19930110 |
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| STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |